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Патент USA US2133282

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‘ Patented
18, 1938
2,133,282
UNITED STATES
PATENT OFFICE
2,133,282 '
PREPARATION OF ALKYLATED AROMATIC
‘
SULPHONIC ACIDS
Alton A. Cook, Glen Ridge, and Swanee V. Val
iavec, Dumont, N. J., assis‘nors to Arkansas
Company, Inc., New York, N. Y., a corporation
of New York
' No Drawing. Application January 17, 1936,
_
Serial No. 59,548
.
7 Claims.
The present invention relates to a process for
preparing alkylated naphthalene sulphonic acids
and their salts and it particularly relates to a
process of preparing novel alkylated naphthalene
sulphonic acids and compositions thereof con
taining between 4 to 8 carbon atoms in the alkyl
group.
‘
,
Although not speci?cally limited thereto, the
present invention will be illustratively described
10 in connection with the production of mono-alkyl,
alpha naphthalene sulphonic acids although it is
to be understood that the present invention is
also applicable to the production of other alkylat
ed sulphonic acids than those speci?cally de
scribed.
It is among the objects of the present invention
to provide an improved process for preparing
alkylated naphthalene sulphonic acids and their
compounds for use as penetrating and wetting
20 out agents and which will be of high stability
and substantial resistance to acids, and calcium
‘ and magnesium salts.
It is another object of the present invention
25
to prepare alkylated naphthalene sulphonic acids
and their compoundswith high yield and without
the production of undesirable Icy-products which
acids are particularly useful in- carbonizing', in
dye baths, in bleaching operations and for in
clusion for soaping, scouring and detergent mix
M30 " tures.
‘a A further'object of the present invention is to
prepare improved alkylated naphthalene sul
phonic acids and their salts which may be di
rectly utilized as penetrating and wetting out
‘agents without requiring an expensive and diiii
cult- puri?cation process and which preparations
may be readily shipped, stored and utilized.
(Cl. 260-505)
may be maintained between 90 to 130° C. with a
preferred range between 100 to 120° C. and for
a time range of from 1 to 5 hours, with a pre
ferred range of from 2 to 3 hours.
-
In the second sulphonation operation, the tem- 5
perature is preferably maintained well below 70°
C. with a preferred range of 40 to 50° C. and for
a. relatively long time say for more than 10 hours
and preferably for less than 20'to 25 hours.
In the second operation it is most desirable to 10
utilize a mixture of concentrated sulphuric acid
and oleum .which will assure ‘substitution of a
sulphonic acid group in the naphthalene nucleus.
It appears as a result of the above process
that only one_ alkyl group enters the nucleus. 15
The exact position of this alhl group has not
been de?nitely determined.
It also appears as a result of the above process,
that a small amount of the beta acid is formed
and this has been found particularly advanta- 20
geous inasmuch as a combination of a relatively
large amount of the alpha with a relatively small
amount of the beta acid is most stable and ef
fective.
As an example of one method of carrying out 25
the invention, naphthalene and secondary butyl
carbinol in equimolecular portions are combined
together in the presence of a large excess of con
centrated sulphuric acid at a temperature of 100
to 120° .C. for a time of approximately 1 to 3 30
hours.
For example, 130 parts by weight of naphtha
lene and 88 parts of secondary butyl carbinol
are mixed together and _385 parts of 66° Bé.
sulphuric acid are added.
35
The mixture is gradually heated until the tem
perature reaches 100° C.
When the reaction has been completed the
during the course of the present speci?cation.
mixture will separate into two layers, the upper
In accomplishing the above objects it has been layer containing the products of condensation 40
40
found that naphthalene may be successfully al
and the lower layer containing a residual acid,
kylated and sulphonated with high yields and “ which lower layer is drawn oil as waste acid.
with the production of only small quantities of
The top layer containing the amylated naph
by-products by ?rst treating the naphthalene thalene is then treated with a mixture of 66° Bé.
with-an alkylating agent in the presence of sul
sulphuric acid and 20% oleum, the mixture for 45
phuric acid, after which the condensation prod-‘ example being made of 100 parts of sulphuric
not is sulphonated at a relatively low temperature, acid and 100 parts of the oleum.
substantially below 70° C.‘ and preferably about
Sulphonation is carried ,out from 16 to 18
40 to 50° C.
' Other objects will be obvious and will appear
50
It. is- found possible in this manner most con
veniently to condense the intermediate aliphatic
alcohols containing from 4 to 8 carbon atoms
with naphthalene and to produce the alphasu1~
phonic acids with a minimum of the beta acids.
In the condensation operation the temperaturev
55
hours at a temperature of from 40 to 50° C.
The resultant sulphonated product is then di- 50
luted with water, say about three times its own
volume, and the diluted mixture is treated with
90 parts of freshly sl'aked lime, which will be
about sufficient to neutralize the free sulphuric
acid.
a‘
2,
aisaaea V
be made in the preparations, times and tempera
The calcium sulphate precipitate resulting is
?ltered o? and the ?ltrate is then treated with
tures speci?ed above and that‘ the process, as de
about 30 parts by weight of sodium carbonate
to form the sodium salt, re?ltered to separate the
precipitated calcium carbonate and evaporated to
scribed, may also be described for the sulphona
tion of other products and it is intended to include
the desired concentration.
all such changes and modi?cations within the
scope of the present invention.
What is claimed is:
1. A process of successively butylating and sul
'
The resulting product is a dark reddish brown
liquid with only a slight odor and marked form~
ing properties and contains from 20 to 50% of
phonating aromatic compounds which comprises
butylating the aromatic compounds with a butyl 10
alcohol and with a sulphonating agent successive
penetrative properties and will give a test result _ ly at decreasing temperatures, the butylation
of 2 to 3 seconds with a standard sinking test on being carried out at a temperature of 90° to 130°
felt using a 1% solution at 90° F.
. C. and the sulphonation being carried out at a
temperature of between 30° and 60° C.
The solution is particularly suitable for car
15
2. A process of successively amylating and sul
bonizing' since it is highly resistant to'5 Tw. sul
phuric acid (about 4% by weight) which acid is phonating aromatic compounds which comprises
amylating aromatic compounds with an amyl al
largely used for carbonizing.‘
Even after heating at 150°-180° F. for several ' cohol and with a sulphonating agent successively
10
the alkylated naphthalene sulphonic acid.
The product produced has high wetting and
20 hours there' is no clouding or precipitation.
at decreasing temperatures, the amylation being
The compound has a highresistance to cal
cium chloride and it will stand up to 2 parts of
calcium chloride to 1 part of the sulphonic acid.
Other alcohols or mixtures of alcohols may be
25 utilized such as normal butyl alcohol, iso-butyl
carried out at a temperature of 90° to 130° C. and
the sulphonation being carried out at a tempera
ture of between 30° and 60° C.
phonating aromatic compounds which comprises
treating the aromatic compounds with an alkyl
ating agent and with a sulphonating agent suc
carbinol, (or normal amyl'alcohol) iso-butyl car
cessively at decreasing temperatures, the alkyla
binol, methyl propyl carbinol, diethyl carbinol,
dimethyl ethyl carbinol, tertiary amyl alcohol,
30 normal hexyl'alcohol, methyl amyl alcohol, 2
ethyl butyl alcohol and octyl alcohol, (2-ethyl
tion being carried out ata temperature of 90° to
130° C. and the sulphonation being carried out 30
at a temperature of between 30° and 60° 0., the
alkylating agent consisting of one or more ali
hexanol) .
phatic alcohols having from 4 to 8 carbon atoms.
‘The octyl and hexyl alcohols require a some
4. A process of producing mono alkyl alpha
what higher proportion of sulphuric acid than the
naphthalene sulphonic acids which comprises 35
combining naphthalene and an aliphatic alcohol
secondary butyl carbinol in the alkylation step. ‘
In the preferred product the beta product
forms between 5 to 20% of the sulphonic acid
in the presence of sulphuric acid at a temperature
of 100° to 120° C. and then increasing the con
while the alpha ranges from 95 to 80%‘ of the sul
phonic acid.
'
3. A process of successively alkylating and sul
alcohol, secondary butyl alcohol, normal butyl
40
20
I centration of sulphuric acid and sulphonating at
‘
a temperature of 40° to 50° C.
The above process may be illustrated by the fol
40
5. A process of producing mono alkyl alpha
lowing equations:
naphthalene sulphonic acids which comprises
combining naphthalene and an aliphatic alcohol
in the presence of sulphuric acid at a tempera—
ture of 100° to 120° C. and then increasing the
45
concentration of sulphuric acid and sulphonat
ing at a temperature of 40° to 50° 0., said aliphatic
' alcohol containingfrom 4 to 8 carbon atoms.
I
V 6. A process of producing mono alkyl alpha
naphthalene sulphonic acids which comprises <
50
combining naphthalene and an aliphatic ‘alcohol
in the presence of sulphuric acid at a tempera
ture of 100° to 120° C. and then increasing the
concentration of sulphuric acid and sulphonating
The sulphonation and/or allgvlation operations
described above may, in certain instances, be
55 also applied to alkylation with less than four, or
more than eight carbon atoms and/or to the
treatment of other cyclic hydrocarbons or heter
ocyclic materials than naphthalene, such as cyclo
at a temperature of 40 to 50° C., said naphthalene ‘ 1
and aliphatic alcohol being used in equi-molecu
lar proportions.
,
<
7. A process of producing mono alkyl alpha
naphthalene sulphonic acid which comprises re
hexane, pyridine, quinolin, benzene, toluene, xy
lene, anthracene, phenanthrene, terpenes, (e. g.
acting about equimolecular weights of naphtha
60
pine oil) and so forth, which hydrocarbons may T lene and a lower alkanol having between 4 and 8
carbon atoms together in the presence of sul
be substituted, if desired, by sulpho, a1kyl-, aral
phuric acid at‘ a temperature between 100 and
kyl, alicyclic-, heterocyclic-, nitrohalogen, car
120° C. and then reacting the alkylated naphtha
boxy, ester, ether or other groupings and/or hy
lene with- a sulphonating reagent containing 65
drogenated.
'
oleum at a temperature between 40° and 50° C.
Mixtures of the various materials above men
to form the alpha-sulphonic acid.
tioned may be alkylated and/or sulphonated ac
cording to the above procedures and if desired in
certain cases the steps may be reversed.
70
It is to be understood that many changes may
_
ALTON A. COOK.
SWANEE V. VALJAVEC.
70
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